KR20240065223A - Method for preparing organic sulfur compounds - Google Patents

Abstract

The present invention relates to a method for producing an organic sulfur compound, and more specifically, to synthesize an organic sulfur compound by reacting a specific compound with a metal hypohalite in the presence of a reaction solvent and a ruthenium catalyst, wherein the reaction solvent is a water-insoluble organic solvent alone. , or a mixed solvent containing water and a water-soluble organic solvent is used, wherein the water-insoluble organic solvent and the water-soluble organic solvent are polar aprotic organic solvents having a dielectric constant of 30 or less. It relates to a method for producing sulfur compounds.
According to the present invention, the reaction stability is excellent, the reaction time is shortened, side reactions are low, so the yield of organic sulfur compounds is high, and by using an organic solvent capable of layer separation with water as a reaction solvent, the solvent recovery rate is high and the solvent It has the effect of providing a method for producing reusable organic sulfur compounds.

Description

Method for producing organic sulfur compounds {METHOD FOR PREPARING ORGANIC SULFUR COMPOUNDS}

The present invention relates to a method for producing organic sulfur compounds. More specifically, the present invention relates to an organic solvent that has excellent reaction stability, shortened reaction time, low side reactions, high yield of organic sulfur compounds, and is capable of layer separation with water. This relates to a method for producing an organic sulfur compound that has a high solvent recovery rate and allows reuse of the solvent when used as a reaction solvent.

Organic sulfur compounds using sulfoxide-based compounds (sulfoxide, R-SO-R') and sulfite-based compounds (sulfite, RO-SO-O-R') as starting materials are converted to sulfone-based compounds (sulfone) through redox reactions. , R-SO ₂ -R') and sulfate-based compounds (sulfate, RO-SO ₂ -O-R') can be produced.

The produced sulfone-based compounds (sulfone, R-SO ₂ -R') and sulfate-based compounds (sulfate, RO-SO ₂ -O-R') commonly contain -SO ₂ - forms and are used as fuel additives in industrial processes. It is used as a versatile functional material such as electrolyte solution for lithium ion batteries.

Therefore, efficient and high-yield synthesis methods for sulfone and sulfate compounds are being actively researched. For example, using a sulfoxide-based compound (sulfoxide, R-SO-R') and a sulfite-based compound (sulfite, RO-SO-O-R') as starting materials, sodium hydrogen periodate (NaIO ₄ ) as an oxidizing agent, Technologies using sodium hypochlorite (NaOCl), calcium hypochlorite (Ca(OCl) ₂ ), hydrogen peroxide (HOOH), calcium permanganate (KMnO ₄ ), etc. are known.

In the case of the above oxidizing agents, technology has been proposed to easily store and use them in an aqueous solution due to their high solubility in water. However, due to poor reaction stability or the product being vulnerable to water, purity and yield are rapidly reduced or a heterogeneous (two phase) reaction occurs. There is a problem of poor reproducibility, and in the case of sodium hydrogen periodate (NaIO ₄ ), the unit price is very high, making it unfavorable for industrial use.

As a related document, U.S. Patent No. 6180799 uses a sulfite-based compound (sulfite, RO-SO-O-R') as a starting material according to the following reaction formula 1, uses acetonitrile and water as reaction solvents, and uses an oxidizing agent. Ro discloses a technology for producing a sulfate-based compound (sulfate) using sodium hydrogen periodate (NaIO ₄ ).

[Scheme 1]

However, since acetonitrile (MeCN) used as a reaction solvent is a water-miscible solvent, it is difficult to separate acetonitrile from water after the reaction, making purification difficult and reusing the solvent. In addition, the process cost increases due to the use of the expensive oxidizing agent described above. There is a downside.

Accordingly, technology using methylene chloride, dichloroethane, dimethyl carbonate, etc. as reaction solvents has been developed, but in this case, it is difficult to apply from a process perspective due to low reaction yield and solvent recovery due to reaction delay, so it is easy to purify while increasing reaction yield. There is a need to develop technology that uses oxidizing agents that can easily reuse solvents and replace expensive oxidizing agents.

In order to solve these problems of the prior art, the present invention aims to provide a method for producing organic sulfur compounds using an oxidizing agent that increases the reaction yield, is easy to purify, allows easy solvent reuse, and can replace expensive oxidizing agents. .

The above and other objects of the present invention can all be achieved by the present invention described below.

In order to achieve the above object, the present invention

In the presence of a reaction solvent and a ruthenium catalyst, one or more compounds selected from among the compounds represented by the following formulas 1-1 to 1-2 are reacted with a metal hypohalite to produce the following formulas 2-1 to 2-2. Synthesize one or more compounds selected from one or more compounds selected from among the compounds,

The reaction solvent is a water-insoluble organic solvent alone or a mixed solvent containing water and a water-soluble organic solvent.

A method for producing an organic sulfur compound is provided, wherein the water-insoluble organic solvent and the water-soluble organic solvent are polar aprotic organic solvents having a dielectric constant of 30 or less.

[Formula 1-1 to 1-2]

[Formula 2-1 to 2-2]

(In the above formulas _1-1 , 1-2, 2-1 and 2-2 _, X _{1 ,} In the case R ₁ , R ₂ , R ₁ ' and R ₂ ' are each independently hydrogen, substituted or unsubstituted alkyl having 1 to 10 carbon atoms, and when n is an integer of 1 to 4, R ₁ , R ₂ , R ₁ ' and R ₂ ' are each independently a bond, substituted or unsubstituted alkylene having 1 to 10 carbon atoms.)

In addition, the present invention reacts a liquid metal hypohalite with a compound represented by the following formula 1-1 or 1-2 in the presence of a reaction solvent, a ruthenium catalyst, and a weak base to produce a compound represented by the formula 2-1 or 2-2. Synthesized, wherein the reaction solvent includes an organic solvent represented by the following Chemical Formula 3-1 or Chemical Formula 3-2,

[Formula 3-1]

[Formula 3-2]

Before adding the liquid metal hypohalite, the ruthenium catalyst and the weak base are added,

The weak base provides a method for producing an organic sulfur compound, characterized in that the pH is adjusted to 8 to 9.

In addition, the present invention,

Preparing a reactant solution by mixing a reaction solvent and one or more compounds selected from the compounds represented by the following formulas 1-1 to 1-2;

Adding a ruthenium catalyst and a weak base to the reactant solution;

Synthesizing one or more compounds selected from the compounds represented by the following formulas 2-1 to 2-2 by adding metal hypohalite to the reactant solution containing the ruthenium catalyst and the weak base; and

It includes the step of separating layers of one or more compounds selected from the compounds represented by Formulas 2-1 to 2-2 and then purifying the supernatant by distillation,

The reaction solvent is a water-insoluble organic solvent alone or a mixed solvent containing water and a water-soluble organic solvent.

A method for producing an organic sulfur compound is provided, wherein the water-insoluble organic solvent and the water-soluble organic solvent are polar aprotic organic solvents having a dielectric constant of 30 or less.

In addition, the present invention includes the steps of preparing a reactant solution by mixing a reaction solvent and a compound represented by Formula 1-1 or 1-2;

Adding a ruthenium catalyst and a weak base to the reactant solution;

Synthesizing a compound represented by the following formula 2-1 or 2-2 by adding liquid metal hypohalite to the reactant solution containing the ruthenium catalyst and the weak base; and

It includes the step of separating the layers of the compound represented by Formula 2-1 or 2-2 and then purifying the supernatant by distillation,

The reaction solvent includes an organic solvent represented by the following Chemical Formula 3-1 or Chemical Formula 3-2,

[Formula 3-1]

[Formula 3-2]

Before adding the liquid metal hypohalite, the ruthenium catalyst and the weak base are added,

The weak base provides a method for producing an organic sulfur compound, characterized in that the pH is adjusted to 8 to 9.

[Formula 1-1 to 1-2]

[Formula 2-1 to 2-2]

(In the above formulas _1-1 , 1-2, 2-1 and 2-2 _, X _{1 ,} In the case R ₁ , R ₂ , R ₁ ' and R ₂ ' are each independently hydrogen, substituted or unsubstituted alkyl having 1 to 10 carbon atoms, and when n is an integer of 1 to 4, R ₁ , R ₂ , R ₁ ' and R ₂ ' are each independently a bond, substituted or unsubstituted alkylene having 1 to 10 carbon atoms.)

In addition, the present invention reacts one or more compounds selected from the compounds represented by Formulas 1-1 to 1-2 with metal hypohalite in the presence of a reaction solvent and a ruthenium catalyst to obtain compounds represented by Formulas 2-1 to 2-2. A method for producing an organic sulfur compound is provided, wherein one or more compounds selected from among the compounds are synthesized, and the pH of the reaction solution during the synthesis is 7 to 9.

In addition, the present invention reacts one or more compounds selected from the compounds represented by Formulas 1-1 to 1-2 with metal hypohalite in the presence of a reaction solvent and a ruthenium catalyst to obtain compounds represented by Formulas 2-1 to 2-2. Synthesize one or more compounds selected from the compounds, wherein the metal hypohalite is added in an amount of 1 to 5 equivalents based on 1 equivalent of one or more compounds selected from the compounds represented by Formulas 1-1 to 1-2, A method for producing an organic sulfur compound is provided, wherein the metal hypohalite is calcium hypochlorite, sodium hypochlorite, or a mixture thereof.

Additionally, the present invention provides an organic sulfur compound characterized in that it is obtained by the above-described production method.

According to the present invention, the reaction stability is excellent, the reaction time is shortened, side reactions are low, so the yield of organic sulfur compounds is high, and by using an organic solvent that can separate layers from water as a reaction solvent, the solvent recovery rate is high and the solvent can be reused. This has the effect of providing a method for producing a possible organic sulfur compound.

Figure 1 is a diagram illustrating a reaction mechanism in which water contained in a mixed solvent, which will be described later, reacts with a ruthenium catalyst to activate an oxidation-reduction reaction.
As shown in the black block notation of FIG. 1 described later, the pre-loaded ruthenium catalyst reacts with water (RuCl ₃ + 2H ₂ O) and is converted into tetravalent ruthenium oxide (RuO ₂ ).
The converted tetravalent ruthenium oxide (RuO ₂ ) reacts with metal hypohalite, which is subsequently added according to the two tracks on the left and right of FIG. 1, and one or more of the compounds represented by Formulas 1-1 to 1-2 in a cyclic structure. .
Specifically, tetravalent ruthenium oxide (RuO ₂ ) converted along the right track converts metal hypohalite 2NaOCl to 2NaCl, and reacts with water (2H ₂ O) generated during conversion to form octavalent ruthenium oxide (RuO ₄ ) is converted to
In addition, the octavalent ruthenium oxide (RuO ₄ ) converted along the left track is converted to tetravalent ruthenium oxide (RuO ₂ ) and one or more of the compounds represented by Formulas 1-1 to 1-2 are converted to tetravalent ruthenium oxide (RuO 2 ). It is converted into one or more of the compounds represented by -2.
Figure 2 below is a diagram illustrating the balance of sodium hypochlorite and hypochlorous acid by pH at room temperature.
As shown in Figure 2, which will be described later, it can be seen that sodium hypochlorite is converted to hypochlorous acid when the pH is less than 8 at room temperature. This means that if the pH is not adjusted during the reaction, it may be converted to an acidic mixture, significantly reducing the yield and reaction rate. In addition, the state of the mixture is unstable below pH 7, so it is very difficult to ensure reaction stability, which can lead to an increase in by-products (impurity) and a significantly lower reaction conversion rate. These problems are solved by buffering the decomposition of sodium hypochlorite through pH adjustment using a weak base, providing reaction stability and high yield.
Figure 3 is a diagram examining changes over time when the metal hypohalide used in the present invention is stored under 4°C refrigerated conditions, stored under -10°C frozen conditions, and stored under 20°C room temperature conditions.
Figure 4 is a 1H NMR graph of the compound represented by Chemical Formula 4-7 produced in Example 1 below.

Hereinafter, the method for producing the organic sulfur compound of the present invention will be described in detail with reference to the drawings.

When the present inventors synthesize a predetermined organic sulfur compound from starting materials using a ruthenium catalyst and a metal hypohalite, when a specific reaction solvent is used and the order of addition of the starting materials is specified, the reaction stability is excellent and the reaction time is shortened. It was confirmed that not only was there a low side reaction and the yield of the target material was high, but also the solvent recovery rate was high and the solvent could be reused by using an organic solvent capable of layer separation with water as the reaction solvent. Based on this, the present invention was completed. .

The term "alkyl" used in the present invention includes straight-chain, branched-chain, or cyclic hydrocarbon radicals, and the term "alkylene" refers to a divalent radical derived from alkyl. For example, the alkylene includes methylene, ethylene, isobutylene, cyclohexylene, cyclopentylethylene, 2-propenylene, 3-butynylene, etc.

In the expression "substituted or unsubstituted" used in the present invention, "substituted" means that one or more hydrogen atoms in a hydrocarbon are each, independently of each other, replaced with the same or different substituent.

Here, commonly used substituents may be used, and for example, they are selected from halo, alkyl, aryl, and arylalkyl.

As an example, the method for producing an organic sulfur compound of the present invention is to synthesize a predetermined organic sulfur compound by reacting a starting material with a metal hypohalite in the presence of a reaction solvent and a ruthenium catalyst, wherein the reaction solvent is a water-insoluble organic solvent alone or water and A mixed solvent containing a water-soluble organic solvent is used, and the water-insoluble organic solvent and the water-soluble organic solvent are characterized in that they are polar aprotic organic solvents with a dielectric constant of 30 or less. In this case, the reaction Not only is it excellent in stability, but the reaction time is shortened compared to the prior art, and side reactions are reduced, providing improved output. In addition, by using an organic solvent that can separate layers from water as a reaction solvent, the solvent recovery rate is high and the solvent can be reused. There is.

In this description, unless otherwise specified, the starting material may be one or more compounds selected from compounds represented by Formulas 1-1 to 1-2, which will be described later.

In this description, unless otherwise specified, the material produced from the starting material may be one or more types selected from compounds represented by Formulas 2-1 to 2-2, which will be described later.

Hereinafter, each component required for producing the organic sulfur compound of the present invention will be described in detail.

starting material

For example, the starting material used in the redox reaction in the present disclosure may be selected from one or more compounds represented by the following formulas 1-1 to 1-3.

[Formula 1-1 to 1-3]

In Formulas 1-1 and 1-3 _, X ₁ , X ₃ , X ₄ , X ₁ ' _, is an integer, and when n is 0, R ₁ , R ₃ , R ₄ , R ₁ ', R ₃ ' and R ₄ ' are each independently hydrogen, substituted or unsubstituted alkylene having 1 to 10 carbon atoms, and n is When it is an integer of 1 to 4, R ₁ , R ₃ , R ₄ , R ₁ ', R ₃ ' and R ₄ ' are each independently bonded, substituted or unsubstituted alkylene having 1 to 10 carbon atoms, and at least It may contain one or more carbons.

In _{addition ,} in Formula 1-2 _{, X 2 and} It may be alkyl.

In Formula _{1-1 ,} for example, when X _{1 and}

_In Formula 1-1 _, for example, when X _{1 and} You can.

In Formula _{1-1 ,} for example, when X _{1 and}

_In Formula 1-1 _, for example, when X _{1 and} You can.

In Formula _{1-1 ,} for example, when X _{1 and}

_In Formula 1-1 _, for example, when X _{1 and} You can.

In Formula 1-1 _, for example _, when X _{1 is} methylene and

_In Formula 1-1 _, for example, when X _{1 is} methylene and to 10 alkylene.

Additionally, in Formula _1-2 , for _example , when X _{2 and}

In Formula _{1-2 ,} for example, when X _{2 and}

In Formula 1-2 _, for _example , when X _{2 and}

_In Formula 1-2, for example _, when X _{2 is} methylene and

_In Formula 1-2, for example _, when X _{2 is} methylene and

_In addition, _in Formula 1-3 _, for example _, when X ₃ , X _{4 ,} X ₃ 'and Alternatively, it may be unsubstituted alkylene having 1 to 10 carbon atoms.

_In Formula _1-3 , _for example _, when X ₃ , X _{4 ,} X ₃ 'and It may be alkylene having 1 to 10 carbon atoms.

_In Formula 1-3, for example, when X _{3 and} X _{4 are each} methylene and X ₃ ' _and It may be substituted or unsubstituted alkylene having 1 to 10 carbon atoms.

Additionally, the compounds represented by Formulas 1-1 and 1-2 may be compounds represented by Formulas 1a and 1b below.

[Formula 1a to 1b]

In Formula 1a, R ₁ and R ₁ 'are each independently hydrogen or substituted or unsubstituted alkylene having 1 to 10 carbon atoms, and n may be an integer of 1 to 5.

In Formula 1b, R ₂ and R ₂ 'may each independently be hydrogen or substituted or unsubstituted alkyl having 1 to 10 carbon atoms.

As a specific example, the compounds represented by Formulas 1-1 to 1-3 may be compounds represented by Formulas 1c to 1g below.

[Formula 1c to 1g]

product

For example, the product prepared by using the compounds represented by the formulas 1-1 to 1-2 described above in the redox reaction may be selected from among the compounds represented by the formulas 2-1 to 2-3 below. .

[Formula 2-1 to 2-3]

In Formulas 2-1 and 2-3, X ₁ , X ₃ , X ₄ , _{X 1 ' ,} is an integer, and when n is 0, R ₁ , R ₃ , R ₄ , R ₁ ', R ₃ ' and R ₄ ' are each independently hydrogen, substituted or unsubstituted alkylene having 1 to 10 carbon atoms, and n is When it is an integer of 1 to 4, R ₁ , R ₃ , R ₄ , R ₁ ', R ₃ ' and R ₄ ' are each independently bonded, substituted or unsubstituted alkylene having 1 to 10 carbon atoms, and at least It may contain one or more carbons.

In _{addition ,} in the above formula 2-2, X _{2 and} It is alkyl.

In Formula 2-1 _, for example _, when X _{1 and}

_In Formula 2-1 _, for example, when X _{1 and} You can.

In Formula _{2-1 ,} for example, when X _{1 and}

_In Formula 2-1 _, for example, when X _{1 and} You can.

In Formula 2-1 _, for example _, when X _{1 and}

_In Formula 2-1 _, for example, when X _{1 and} You can.

In Formula 2-1 _, for example _, when X _{1 is} methylene and

_In Formula 2-1 _, for example, when X _{1 is} methylene and to 10 alkylene.

Additionally, in Formula _2-2 , for _example , when X _{2 and}

In Formula 2-2 _, for _example , when X _{2 and}

In Formula 2-2 _, for _example , when X _{2 and}

_In Formula 2-2, for example _, when X _{2 is} methylene and

_In Formula 2-2, for example _, when X _{2 is} methylene and

_In addition, _in Formula 2-3 _, for example _, when X ₃ , X _{4 ,} X ₃ 'and Alternatively, it may be unsubstituted alkylene having 1 to 10 carbon atoms.

_In Formula _2-3 , _for example _, when X ₃ , X _{4 ,} X ₃ 'and It may be alkylene having 1 to 10 carbon atoms.

_In Formula 2-3, for example, when X _{3 and} X _{4 are each} methylene and X ₃ ' _and It may be substituted or unsubstituted alkylene having 1 to 10 carbon atoms.

As a specific example, the compounds represented by Formulas 2-1 and 2-2 may be compounds represented by Formulas 4-1 and 4-2 below.

[Formula 2a to 2b]

In Formula 2a, R ₂ and R ₂ 'may each independently be hydrogen or substituted or unsubstituted alkyl having 1 to 10 carbon atoms.

In Formula 2b, R ₁ and R ₁ 'may each independently be hydrogen or substituted or unsubstituted alkylene having 1 to 10 carbon atoms. At this time, n is an integer from 1 to 5.

Compounds represented by Formulas 2-1 to 2-3 may be compounds represented by Formulas 2c to 2g below.

[Formula 2c to 2g]

oxidation-reduction reaction

The production method according to the present disclosure aims to obtain the compounds represented by the above formulas 2-1 and 2-2 through an oxidation-reduction reaction using the compounds represented by the above-mentioned formulas 1-1 and 1-2 as starting materials. .

The oxidation-reduction reaction will be examined in detail with reference to the reaction mechanism shown in FIG. 1.

Figure 1 below is a diagram illustrating a reaction mechanism in which water contained in a mixed solvent described later reacts with a ruthenium catalyst to activate an oxidation-reduction reaction.

Referring to Figure 1 below, a ruthenium catalyst and a metal hypohalite are used to directly convert the compound represented by Formula 3-3 shown at the bottom left into the compound represented by Formula 4-3 shown at the top left. .

As shown in Figure 1 below, the oxidation-reduction reaction of the present invention provides excellent reaction stability, shortened reaction time, and reduced side reactions by specifying the order of addition of components, types of components, and reaction conditions, and improved yield. In addition, by using an organic solvent that can separate layers from water as a reaction solvent, the solvent recovery rate is high and the solvent can be reused.

Hereinafter, the catalyst, solvent, oxidizing agent, and pH adjuster required for the redox reaction shown in Figure 1 will be examined by dividing them into components, and then the specific conditions and changes over time of the redox reaction will be sequentially examined.

Redox reaction catalyst

In the above-described redox reaction, ruthenium series is added as a catalyst.

Typically, the presence of a catalyst increases the reaction rate because less activation energy is required. Any catalyst that can increase the reaction rate of the redox reaction can be used without limitation, but preferably a platinum group catalyst mainly used as a catalyst for the redox reaction can be used, more preferably a ruthenium group catalyst can be used, Most preferably, ruthenium chloride can be used.

The ruthenium chloride may be used in anhydrous or hydrated form, and the amount used is, for example, 0.0001 to 0.001 equivalents based on 1 equivalent of one or more compounds selected from the compounds represented by Formulas 1-1 to 1-2 , preferably It can be added in the amount of 0.0004 to 0.0006 equivalents, and in this case, the reaction time can be shortened by optimizing the above-described redox reaction, and the reaction yield can be improved without side reactions.

In particular, according to the manufacturing process of the present invention, the reaction proceeds even if the ruthenium chloride is added in a very small amount of 0.0001 to 0.0002 equivalent, so the production cost can be reduced.

Redox reaction oxidizing agent

The oxidizing agent that performs the above-described redox reaction may be a metal hypohalite.

Examples of suitable metal hypohalites include hypohalites of alkali metals or alkaline earth metals.

Alkali metals also participate in the reaction, but compared to only 1 mole of the hypohalite oxidizer of alkali metal, which reacts per mole, 2 moles of OCl ^-1 are released per mole, so even in molar amounts, redox reactions can occur efficiently. You can.

For example, the above-mentioned metal hypohalite can be calcium hypochlorite or sodium hypochlorite (NaOCl). As a specific example, when sodium hypochlorite (12% aqueous solution) is used, water is used under reaction conditions. Since water is included in the aqueous solution even if it is not used, there are no restrictions on performing the redox reaction of this material.

For reference, it is possible to secure up to 50% additional process production compared to prior literature using water. However, it is limited to the case where sodium hypochlorite is used, and the derived value of maximum production may be different when calcium hypochlorite, which exists in a solid state at room temperature, is used.

For reference, changes over time when stored in refrigeration and at room temperature under the same conditions for sodium hypochlorite, which is usually provided in a liquid state, are shown in Figure 3. Figure 3 is a diagram examining changes over time when the metal hypohalide used in the present invention is stored under 4°C refrigerated conditions, stored under -10°C frozen conditions, and stored under 20°C room temperature conditions.

As shown in Figure 3 below, in the case of room temperature storage, there are weaknesses due to long-term storage, but when long-term storage is necessary, frozen storage of sodium hypochlorite is necessary, and storage temperature control (refrigerated storage and frozen storage) It can be seen that changes over time can be minimized.

The amount of the metal hypohalite added is, for example, 1 to 5 equivalents, preferably 2.2 to 4 equivalents, more preferably 2.3 to 3 equivalents, based on 1 equivalent of the compound represented by Formulas 1-1 to 1-2. , most preferably 2.4 to 2.5 equivalents, can optimize the reaction conversion rate and reaction speed.

For reference, in the case of calcium hypochlorite, 2 moles of OCl ^-1 are released per mole, so it is desirable to add half the equivalent amount of sodium hypochlorite.

Redox reaction pH regulator

For example, in the case where sodium hypochlorite is used as the above-mentioned oxidizing agent, sodium hypochlorite has a tendency to easily decompose into hypochlorous acid under conditions of pH 8 or less.

The balance curve of sodium hypochlorite and hypochlorous acid shown by pH at room temperature will be examined in detail with reference to the graph shown in FIG. 2.

Figure 2 below is a diagram illustrating the balance of sodium hypochlorite and hypochlorous acid by pH at room temperature.

As shown in Figure 2 below, when decomposition into hypochlorous acid is buffered through pH adjustment, reaction stability is ensured, which is a major factor in saving time and securing high yield.

In addition, solvent decomposition of acid substances generated during reaction can be minimized by adjusting pH, thereby ensuring solvent stability and high solvent recovery rate.

Therefore, the pH control of this substrate not only provides excellent reaction stability, shortened reaction time, and improved yield due to fewer side reactions, but also has a high solvent recovery rate by using an organic solvent that can separate layers from water as a reaction solvent. This provides the effect of enabling reuse of the solvent.

In the present disclosure, the pH adjuster may be a weak base, preferably an aqueous weak base solution.

The weak base is not limited as long as it does not affect the reaction. For example, sodium (hydrogen) carbonate, ammonium carbonate, potassium carbonate, ammonium phosphate, sodium phosphate, etc. can be used. Considering performance and manufacturing cost, carbonic acid ( It is preferable to use sodium (hydrogen).

The amount of the weak base added is, for example, 0.1 to 1 equivalent, preferably 0.1 to 0.5 equivalent, based on 1 equivalent of one or more compounds selected from the compounds represented by Formulas 1-1 to 1-2 to ensure reaction stability. It is desirable because it can provide stable solvent recovery.

Reaction solvent for redox reaction

The solvent effect is very important in organic reactions, including the redox reactions described above. Even if all other conditions are the same, some reactions may not proceed depending on the solvent, and some reactions may proceed close to 100%. Therefore, selection of a reaction solvent is very important in the method for producing an organic sulfur compound according to the present disclosure.

Since the reaction solvent must be able to dissolve the starting materials, the compounds represented by Chemical Formulas 1-1 and 1-2, it is preferable to use a polar aprotic solvent to control the exothermic reaction caused by water and improve production efficiency. , problems that occur when excessive water is used together as an oxidizing agent and solvent can be minimized.

Meanwhile, the above-described reaction solvent preferably has water-insoluble properties when used alone, and preferably has water-soluble properties when used as a mixed solvent including water. At this time, the water introduced can serve as an activator that activates and promotes the entire redox reaction by oxidizing the ruthenium catalyst, which is the redox reaction catalyst described above.

Referring back to Figure 1 below, the ruthenium catalyst reacts with water and is converted into RuO ₂ , 3HCl, and H+, and among the conversion products, RuO ₂ further reacts with water and is converted into RuO _{4, thereby converting the above-mentioned oxidizing agents, including metal hypohalite, into RuO 4} . It can proceed in two routes: directly react with (right route), or directly react with the compound represented by the above-mentioned formula 3-3 while reducing RuO ₄ to RuO ₂ (left route).

Each route is interconnected and can be specifically explained as follows. That is, as shown in the right route, ruthenium oxide RuO ₂ can be oxidized to RuO ₄ by substituting the hypochlorous acid group of the oxidizing agent with a halogen group, and the RuO ₄ thus produced is reduced to RuO ₂ as shown in the left route, forming Formula 3- It is possible to directly react with the compound represented by 3 to facilitate direct conversion to the compound represented by Chemical Formula 4-3, thereby shortening the reaction time, improving the reaction yield without side reactions, and also providing reaction stability.

The amount of water used is, for example, 10 to 1,500 parts by weight, preferably 30 to 1,000 parts by weight, more preferably, based on 100 parts by weight of one or more compounds selected from the compounds represented by Formulas 1-1 to 1-2. It is preferable to add 50 to 500 parts by weight to optimize reaction conversion rate and purity.

In particular, the weight ratio of water and organic solvent constituting the mixed solvent is also an important factor affecting the yield and conversion rate of the redox reaction of the present invention.

For example, the weight ratio of the mixed solvent is 1:10 or more (water:organic solvent), 1:20 to 1:30 (water:organic solvent), 1:25 to 1:40 (water:organic solvent), 1: A ratio of 20 to 1:40, or 1:20 to 1:30 (water: organic solvent) is preferred as it can optimize reaction speed and reaction efficiency.

The reaction solvent used in the present disclosure may be, for example, a polar aprotic organic solvent with a dielectric constant of 30 or less, and is preferably a polar aprotic organic solvent with a dielectric constant of 20 or less. It may be a solvent, and more preferably a polar aprotic organic solvent having a dielectric constant of 5 to 15.

The solvent may be a polar aprotic solvent represented by the following formula (3).

[Formula 3]

(In the above formula (3),

Specific examples of the above-described polar aprotic organic solvent having a dielectric constant of 30 or less include ethyl acetate, methyl isobutyl ketone, acetone, methyl ethyl ketone, methyl butyl ketone, 2-pentanone, cyclopentanone and 2-heptanone. can be selected from among.

The reaction solvent may preferably be ethyl acetate, methyl isobutyl ketone, or a mixture thereof. For reference, ethyl acetate has water-insoluble properties and satisfies a dielectric constant of 5.9, and methyl isobutyl ketone has water-insoluble properties and satisfies a dielectric constant of 13.11.

In this description, the dielectric constant is known as the relative dielectric constant and is equal to the ratio of the capacitance of a capacitor filled with a material to the capacitance of the same capacitor in a vacuum without dielectric material.

로 표시된 유전 상수는 간단히

=C/C0로 표현된다. 유전 상수는 차원이 없는 수이다. Specifically, if C is the value of the capacitance of a capacitor filled with a given dielectric and C0 is the capacitance of the same capacitor in a vacuum, then the Greek letter kappa,

The dielectric constant denoted by is simply

It is expressed as =C/C0. The dielectric constant is a dimensionless number.

에서 얻었고, 예를 들어, "Handbook of Chemistry and Physics", David R. Lide, CRC, 83 rd Edition, 2002-2003과 같은 화학 편람에서 확인될 수 있다.For purposes of this detailed description and claims, the dielectric constant value of the solvents used in the present invention is 20

Obtained from and can be found, for example, in chemical handbooks such as "Handbook of Chemistry and Physics", David R. Lide, CRC, 83 rd Edition, 2002-2003.

Conditions and changes over time of oxidation-reduction reaction

The dropping temperature of the metal hypohalite is, for example, -10 to 65°C, -10 to 40°C, -10 to 20°C, or -10 to 5°C, which is appropriate for providing reaction stability.

At this time, the dropping time of the metal hypohalite is, for example, 45 minutes or less, preferably 5 to 40 minutes, and more preferably 10 to 40 minutes. In this case, the reaction time is shortened while the yield is improved.

For example, when the production reaction scale of the organic sulfur compound is 1kg or more, the metal hypohalite is appropriately added dropwise under temperature conditions of 0 to 5°C for pilot and mass production applications.

For example, when the production reaction scale of the organic sulfur compound is 1 kg or more, the metal hypohalite is added dropwise for 6 hours or less, preferably 5 hours or less, and more preferably 3 to 4 hours. This is the reaction time for pilot and mass production applications. It has the effect of improving yield while shortening the process.

The reaction temperature during the synthesis may be, for example, 0 to 25°C, 0 to 20°C, 0 to 15°C, or 0 to 5°C to achieve the optimal reaction effect.

In addition, considering the reaction efficiency, the reaction temperature during the synthesis is preferably within the suggested reaction temperature range by maintaining the dropping temperature of the metal hypohalite described above.

During the synthesis, the reaction time is preferably 8 hours or less, preferably 6 hours or less, and more preferably 4 hours or less to optimize reaction efficiency.

Meanwhile, the pH of the reaction during the synthesis is preferably controlled to, for example, 7 to 9, preferably 8 to 9, and more preferably 8.5 to 9 using the above-mentioned pH adjuster to optimize reaction efficiency.

In this description, pH can be measured by a measurement method commonly used in the technical field to which the present invention pertains.

For example, the method for producing an organic sulfur compound according to the present disclosure includes preparing a reactant solution by mixing the mixed solvent with one or more compounds selected from the compounds represented by Formulas 1-1 to 1-2; Adding a ruthenium catalyst to the reactant solution; And it is characterized in that metal hypohalite is added to the reactant solution into which the ruthenium catalyst is added. In this case, reaction stability is excellent, reaction time is shortened, side reactions are reduced, so not only is the yield improved, but layer separation with water is possible. By using an organic solvent as a reaction solvent, the solvent recovery rate is high and the solvent can be reused.

In fact, according to the method for producing an organic sulfur compound according to the present disclosure, the purity of the compounds represented by Formulas 2-1 to 2-2 within 2 hours of reaction time is, for example, 90% by weight or more, preferably 95% by weight or more, More preferably, it may be 99% by weight or more, and most preferably, it may be 99.8% by weight.

In addition, according to the method for producing an organic sulfur compound according to the present disclosure, the yield of the compounds represented by Formulas 2-1 to 2-2 within 2 hours of reaction time is, for example, 79% by weight or more, preferably 80% by weight or more, More preferably, it may be 85% by weight or more, more preferably 90% by weight or more, and most preferably 95% by weight or more.

After reacting for 2 hours according to the method for producing an organic sulfur compound according to the present disclosure, the reaction was terminated, and the purity of the product as measured by gas chromatography was 99.8%.

In addition, according to the manufacturing method of the present disclosure, as described above, the product is obtained with a high purity of 99.8% by weight or close thereto, and does not contain insoluble impurities, so a quench reagent is used without post-processing such as filter treatment or filtrate purification. ) can be added to terminate the reaction. At this time, hydrogen peroxide may be used as the reaction termination reagent.

Furthermore, according to the manufacturing method of the present invention, layer separation from water is possible, so solvent recovery is easy, and the solvent recovery rate through distillation can be, for example, 90% or more, preferably 95% or more.

According to another embodiment of the present invention, in the presence of a reaction solvent and a ruthenium catalyst, at least one compound selected from the compounds represented by Formulas 1-1 to 1-2 is reacted with a metal hypohalite to obtain Formulas 2-1 to 2-1. Preparing a reactant solution by synthesizing one or more compounds selected from the compounds represented by 2-2 and mixing the mixed solvent with one or more compounds selected from the compounds represented by Formulas 1-1 to 1-2; Adding a ruthenium catalyst to the reactant solution; and adding a metal hypohalite to the reactant solution containing the ruthenium catalyst.

In this description, the weight ratio of the mixed solvent, reaction conditions, and content of metal hypohalite are the same as those described above, so repeated descriptions are omitted.

According to another embodiment of the present invention, preparing a reactant solution by mixing a reaction solvent and at least one compound selected from compounds represented by the following formulas 1-1 to 1-2;

Adding a ruthenium catalyst and a weak base to the reactant solution;

Synthesizing one or more compounds selected from the compounds represented by the following formulas 2-1 to 2-2 by adding metal hypohalite to the reactant solution containing the ruthenium catalyst and the weak base; and

It includes the step of separating layers of one or more compounds selected from the compounds represented by Formulas 2-1 to 2-2 and then purifying the supernatant by distillation,

The reaction solvent is a water-insoluble organic solvent alone or a mixed solvent containing water and a water-soluble organic solvent, and the water-insoluble organic solvent and the water-soluble organic solvent are polar amphoteric substances having a dielectric constant of 30 or less. A method for producing an organic sulfur compound characterized as a magnetic organic solvent is provided.

In Formulas _1-2 and _2-2 , X _{2 and} It is an alkyl of 10.

In this description, the weight ratio of the mixed solvent, addition order, reaction conditions, and content of metal hypohalite are the same as those described above, so repeated descriptions are omitted.

According to another embodiment of the present invention, in the presence of a reaction solvent and a ruthenium catalyst, at least one compound selected from the compounds represented by Formulas 1-1 to 1-2 is reacted with a metal hypohalite to obtain Formulas 2-1 to 1-2. A method for producing an organic sulfur compound is provided, wherein at least one compound selected from the compounds represented by 2-2 is synthesized, and the pH of the reaction solution during the synthesis is 7 to 9.

In this description, the mixed solvent content ratio, addition order, reaction conditions, and metal hypohalite content are the same as those described above, so repeated descriptions are omitted.

According to another embodiment of the present invention, an organic sulfur compound is provided, characterized in that it is obtained by the above-described production method.

Hereinafter, preferred embodiments are presented to aid understanding of the present invention. However, the following examples are merely illustrative of the present invention, and it is clear to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention. It is natural that such variations and modifications fall within the scope of the attached patent claims.

[Example]

Example 1

A thermometer was installed in a 5L 4-neck reaction vessel, 100 g of the compound represented by the following formula 3-7 (hereinafter also referred to as 'starting material') and 3000 g of methyl isobutyl ketone were added and cooled to 0°C. The pH of the reaction solution was maintained at about pH 8.3 by adding a 12% aqueous solution of sodium bicarbonate.

[Formula 3-7]

Next, 0.0006 equivalents of ruthenium chloride were added based on 1 equivalent of the starting material and stirred.

While the temperature was maintained at 0°C, sodium hypochlorite at a concentration of 13.5% by weight was added dropwise in an amount of 2.5 equivalents based on 1 equivalent of the starting material to maintain the temperature of the reaction solution at 0 to 5°C.

As a reaction termination reagent, 0.2 equivalents of hydrogen peroxide was added based on 1 equivalent of the starting material, stirred for 30 to 60 minutes, and then layer separation was performed. The separated filtrate was filtered using a Celite filter, and the reaction solution was concentrated and recrystallized to obtain a solid product. The yield was calculated to be 90% by weight.

As a result of ¹ H NMR analysis of the solid product, it was confirmed that it was a compound represented by the following formula 4-7 (see FIG. 4).

Subsequently, the product was obtained after vacuum drying at 80°C, gas chromatography was performed, and the purity of the compound represented by the following formula 4-7 (hereinafter also referred to as the product) was confirmed and the purity was 99.7% by weight.

[Formula 4-7]

In addition, in the above step, the filtrate was separated into layers and concentrated under normal pressure for 2 hours. The recovery rate of the solvent methyl isobutyl ketone was confirmed to be 90% by weight.

From the above results, it can be seen that when appropriate input materials and input sequence are used, and when a specific organic solvent capable of separating water and layers is used, not only is the recovery rate of the organic solvent high, but also provides reproducible yield and purity even when the recovery solvent is used. there was.

Example 2

A thermometer was installed in a 5L 4-neck reaction vessel, 2000g of ethyl acetate and 100g of the compound represented by the following formula 3-7 (hereinafter referred to as 'starting material') were added and cooled to 0°C. The pH of the reaction solution was maintained at about pH 8.3 by adding a 12% aqueous solution of sodium bicarbonate.

[Formula 3-7]

Next, 0.0004 equivalents of ruthenium chloride were added based on 1 equivalent of the starting material and stirred.

While the temperature was maintained at 0℃, sodium hypochlorite at a concentration of 13.5% by weight was added dropwise at 3℃ at 2.5 equivalents based on 1 equivalent of the starting material to maintain the reaction solution temperature at 0~5℃, and the pH of the reaction solution was A 12% aqueous solution of sodium bicarbonate was added to maintain pH around 8.3.

As a reaction termination reagent, 0.2 equivalents of hydrogen peroxide was added based on 1 equivalent of the starting material, stirred for 30 to 60 minutes, and then layer separation was performed. The separated filtrate was filtered using a Celite filter, and the reaction solution was concentrated and recrystallized to obtain a solid product. The yield was calculated to be 94% by weight.

Subsequently, the product was obtained after vacuum drying at 80°C, gas chromatography was performed, and the purity of the compound represented by the following formula 4-7 (hereinafter also referred to as the product) was confirmed and the purity was 99.7% by weight.

[Formula 4-7]

In the above step, the filtrate was separated into layers and concentrated under normal pressure for 2 hours. The recovery rate of the solvent ethyl acetate was checked and found to be 90% by weight.

From the above results, it can be seen that when appropriate input materials and input sequence are used, and when a specific organic solvent capable of separating water and layers is used, not only is the recovery rate of the organic solvent high, but also provides reproducible yield and purity even when the recovery solvent is used. there was.

Example 3

As a result of repeating the same process as Example 2 except that 1900 g of ethyl acetate recovered in Example 2 was used as a solvent, the yield was 94% by weight, which is equivalent to or similar to that in Example 2, The purity was also confirmed to be 99.7%.

From the above results, it can be seen that when appropriate input materials and input sequence are used, and when a specific organic solvent capable of separating water and layers is used, not only is the recovery rate of the organic solvent high, but also provides reproducible yield and purity even when the recovery solvent is used. there was.

Examples 4 to 7

The same process as Example 1 was repeated except that the compound represented by Chemical Formula 3-7 used as a starting material in Example 1 was replaced with [Formula 3-3 to 3-6], respectively.

[Formula 3-3 to 3-6]

The structures, ¹ H NMR analysis results, and FD-MS analysis results of the products obtained in Examples 4 to 7 are shown in Table 1 below, respectively.

chemical formula structure NMR (CDCl3), 300 MHz FD-MS 4-3 4.77(4H,s) m/z = 123.98
C ₂ H ₄ O ₄ S = 124.11 4-4 6.40(3H,d), 5.14(1H,m), 4.75(1H,dd), 4.32(1H,t) m/z = 138.00
C ₃ H ₆ O ₄ S = 138.14 4-5 4.89(2H,d), 4.64(2H,d) m/z = 231.93
C ₃ H ₄ O ₈ S ₂ = 232.18 4-6 3.75~3.73(4H,t), 1.72~1.69(2H,m) m/z = 138.00
C ₃ H ₆ O ₄ S = 138.14 4-7 4.93(8H,s) m/z = 259.97
C ₅ H ₈ O ₈ S ₂ = 260.23

Comparative Example 1

A thermometer was installed in a 5L four-necked reaction vessel, and 100 g of the compound represented by the following formula 3-7 (hereinafter also referred to as 'starting material'), 1570 g of acetonitrile, and 6580 g of water were added and cooled to 0°C.

[Formula 3-7]

Next, 0.001 equivalents of ruthenium chloride were added based on 1 equivalent of the starting material and stirred.

While the temperature was maintained at 0°C, sodium hypochlorite at a concentration of 13.5% by weight was added dropwise at 3°C in the amount of 4 equivalents based on 1 equivalent of the starting material to maintain the temperature of the reaction solution at 0 to 5°C.

As a reaction termination reagent, 0.2 equivalents of hydrogen peroxide were added based on 1 equivalent of the starting material, stirred for 30 to 60 minutes, and layer separation was performed without a reaction termination reagent. The separated filtrate was filtered using a Celite filter, and the reaction solution was Concentration and recrystallization gave a solid product, and the calculated yield was 60% by weight.

Subsequently, the product was obtained after vacuum drying at 80°C, gas chromatography was performed, and the purity of the compound represented by the following formula 4-7 (hereinafter also referred to as the product) was confirmed and the purity was 94% by weight.

[Formula 4-7]

In the above step, the filtrate was separated into layers and concentrated under normal pressure for 2 hours. The recovery rate of the solvent acetonitrile was checked and found to be 60%. However, upon checking the recovered acetonitrile, it was confirmed that it contained water and was difficult to reuse.

Compared to Example 1, it was found that in the case of Comparative Example 1 in which the appropriate type was not used even when mixed solvents were used, it was difficult to apply an efficient purification process and the purity decreased to 95% or less.

Comparative Example 2

The same process as Example 1 was repeated except that the reaction was carried out for 5 days without using water, and the yield was confirmed to be 20% by weight.

Compared to Example 1, in Comparative Example 2, where an organic solvent was used for a long time instead of a mixed solvent, it was found that the yield decreased to 20% by weight due to a decrease in production amount due to the non-use of water.

Comparative Example 3

As a result of repeating the same process as Example 1, except that water was not used and the reaction was carried out for 4 days while maintaining the reaction solution temperature at 31°C, which is higher than 30°C, the yield was 5 weight. It was confirmed that it was less than %.

Compared to Example 1, in the case of Comparative Example 3, in which a mixed solvent was not used and an organic solvent was used under an inappropriate reaction temperature for a long time, the amount produced due to the absence of water was extremely reduced, and the yield fell to less than 5% by weight. I was able to.

Reference examples 1 to 2

The same process as Example 1 was repeated except that the pH of the reaction solution was changed as shown in Table 1 below, and the yield of the obtained product was measured and shown in Table 2 below.

division Reaction solution pH Yield (% by weight) Example 1 8.3 90 Reference example 1 6 50 Reference example 2 5 38

As shown in Table 2, when the pH of the reaction solution in Example 1 was within the range of 7 to 9, the yield was 90% by weight, but in Reference Examples 1 and 2 where the pH was maintained at 6 or 5, respectively, the yield was 50 to 38% by weight. It was only %.

In particular, it was found that the yield of Comparative Example 2 using pH 5 dropped sharply compared to Example 1 using pH 8.3.

Reference examples 3 to 4

The same process as Example 1 was repeated except that the input order in Example 1 was changed as shown in Table 2 below, and the yield of the obtained product was measured and shown in Table 3 below.

Input order transference number
(weight%) division Organic solvent + water starting material RuCl ₃ NaOCl Example 1 One 2 3 4 90 Reference example 3 One 4 3 2 10

(In the table above, the numbers 1, 2, 3, and 4 are the input order, and the smallest number is input first.)

As shown in Table 3, in the case of the input order of Example 1 (mixed solvent -> starting material -> ruthenium catalyst -> metal hypohalite), the yield was 90% by weight, but the input order was mixed solvent -> metal hypohalite. In the case of Reference Example 3 where halite -> ruthenium catalyst -> starting material was changed, the yield was only 10% by weight.

Reference example 5

For sodium hypochlorite (concentration 13.9% by weight) provided in liquid form in Example 1, the storage temperature was changed to 4°C, -10°C, and 20°C, respectively, for 1 day, 7 days, 14 days, 21 days, and 30 days. The change in content was confirmed over time, and the results are shown in Table 4 and Figure 3 below.

storage temperature
Storage period -10℃ 4℃ 20℃ 1 day (% by weight) 13.9 13.9 13.9 7 days (% by weight) 13.9 13.2 12.6 14 days (% by weight) 13.8 13.1 12.1 21 days (% by weight) 13.7 13.1 11.9 30 days (% by weight) 13.7 13.0 11.4

As shown in Table 4 above, as a result of the time-lapse test by temperature, the sodium hypochlorite aqueous solution with a concentration of 13.9% by weight was measured to be 11.4% by weight after 30 days at 20°C, confirming the shortcomings of long-term storage.

In contrast, it was measured to be 13.0% by weight after 30 days at 4℃ and 7% by weight after 30 days at -10℃, showing that changes over time that occur when stored at room temperature can be minimized by controlling the storage temperature. You can.

In conclusion, in the presence of a reaction solvent and a ruthenium catalyst, a starting material is reacted with a metal hypohalite to synthesize a given organic sulfur compound, but when a polar aprotic organic solvent having a specific dielectric constant is used as the reaction solvent, the reaction is stable. It was confirmed that not only was this excellent, but the reaction time was shortened, the yield was improved due to less side reactions, and the solvent recovery rate was high and the solvent could be reused by using an organic solvent capable of layer separation from water as the reaction solvent.

Claims (10)

In the presence of a reaction solvent, a ruthenium catalyst, and a weak base, a compound represented by the following formula 1-1 or 1-2 is reacted with a liquid metal hypohalite to synthesize a compound represented by the following formula 2-1 or 2-2,
The reaction solvent includes an organic solvent represented by the following Chemical Formula 3-1 or Chemical Formula 3-2,
[Formula 3-1]

[Formula 3-2]

Before adding the liquid metal hypohalite, the ruthenium catalyst and the weak base are added,
A method for producing an organic sulfur compound, characterized in that the weak base is adjusted to pH 8 to 9.
[Formula 1-1 to 1-2]

[Formula 2-1 to 2-2]

(In the above formulas _1-1 , 1-2, 2-1 and 2-2 _, X _{1 ,} In the case R ₁ , R ₂ , R ₁ ' and R ₂ ' are each independently hydrogen, substituted or unsubstituted alkyl having 1 to 10 carbon atoms, and when n is an integer of 1 to 4, R ₁ , R ₂ , R ₁ ' and R ₂ ' are each independently a bond, substituted or unsubstituted alkylene having 1 to 10 carbon atoms.) According to clause 1,
A method for producing an organic sulfur compound, wherein the reaction solvent contains a weak base. According to clause 2,
A method for producing an organic sulfur compound, characterized in that the weak base is added in an amount of 0.1 to 1 equivalent based on 1 equivalent of the compound represented by Formula 1-1 or 1-2. According to clause 1,
A method for producing an organic sulfur compound, wherein the ruthenium catalyst is ruthenium chloride. According to clause 1,
A method for producing an organic sulfur compound, wherein the ruthenium catalyst is added in an amount of 0.0001 to 0.001 equivalents based on 1 equivalent of the compound represented by Formula 1-1 or 1-2. According to clause 1,
A method for producing an organic sulfur compound, characterized in that the liquid metal hypohalite is at least one selected from sodium hypochlorite and calcium hypochlorite. According to clause 1,
A method for producing an organic sulfur compound, characterized in that the liquid metal hypohalite is added in an amount of 1 to 5 equivalents based on 1 equivalent of the compound represented by Formula 1-1 or 1-2. According to clause 1,
A method for producing an organic sulfur compound, characterized in that the reaction temperature during the synthesis is -10 to 65 ℃. According to clause 1,
Preparing a reactant solution by mixing the reaction solvent and the compound represented by Formula 1-1 or 1-2; Adding a ruthenium catalyst to the reactant solution; and adding liquid metal hypohalite to the reactant solution containing the ruthenium catalyst. Preparing a reactant solution by mixing a reaction solvent and a compound represented by Formula 1-1 or 1-2;
Adding a ruthenium catalyst and a weak base to the reactant solution;
Synthesizing a compound represented by the following formula 2-1 or 2-2 by adding liquid metal hypohalite to the reactant solution containing the ruthenium catalyst and the weak base; and
It includes the step of separating the layers of the compound represented by Formula 2-1 or 2-2 and then purifying the supernatant by distillation,
The reaction solvent includes an organic solvent represented by the following Chemical Formula 3-1 or Chemical Formula 3-2,
[Formula 3-1]

[Formula 3-2]

Before adding the liquid metal hypohalite, the ruthenium catalyst and the weak base are added,
A method for producing an organic sulfur compound, characterized in that the weak base is adjusted to pH 8 to 9.
[Formula 1-1 to 1-2]

[Formula 2-1 to 2-2]

(In the above formulas _1-1 , 1-2, 2-1 and 2-2 _, X _{1 ,} In the case R ₁ , R ₂ , R ₁ ' and R ₂ ' are each independently hydrogen, substituted or unsubstituted alkyl having 1 to 10 carbon atoms, and when n is an integer of 1 to 4, R ₁ , R ₂ , R ₁ ' and R ₂ ' are each independently a bond, substituted or unsubstituted alkylene having 1 to 10 carbon atoms.)